α-nitration of ketones via enol silyl ethers. Radical cations as reactive intermediates in thermal and photochemical processes

Journal of Organic Chemistry

Volumn 61, Issue 2, 1996, Pages 627-639

  Rathore, Rajendra ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000318373     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9515687     Document Type: Article

References (93)

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60. (a) A similar spectral transient was observed when either tetracyanobenzene or maleic anhydride excited singlet was quenched with enol silyl ether 7 (unpublished results, S. Hubig).
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66. The method is also potentially applicable to other carbonyl compounds such as aldehydes, esters, etc. For example, see Fukuzumi et al. in ref 25.
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70. 2 group is (presumably) involved in the charge-transfer interaction. An X-ray crystallographic determination of a TNM charge-transfer complex would establish this point.
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72. (a) Compare Masnovi, J. M., Kochi, J. K.; Hilinski, E. F.; Rentzepis, P. N. J. Am. Chem Soc. 1986, 108, 1126.
73. (b) Note that the direct photoexcitation of the EDA complex by irradiation of the charge-transfer band allows the nitration in high yields of such relatively poor donors as the enol silyl ethers 3a, Sb, and 4a even at low temperatures.
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77. (a) Compare the TMS transfer in the related (chloraml) charge-transfer process, as described by Bockman, T. M. et al. in ref 33b.
78. (b) Although the alternative sequence (involving TMS transfer in the ion pair, followed by homolytic coupling) cannot be rigorously discounted, it is disfavored since it does not readily account for the difference in nitro ketone yield between the isomeric 1a and 7.
79. • toward reactive aromatic radical cations is described in ref 47.
80. With thermal activations, the steady-state concentrations of reactive intermediates are generally so low as to make their detection experimentally difficult to observe.
81. •. [For a discussion of this important point, see Savéant, J.-M. J. Am. Chem. Soc. 1987, 209, 6788.]
82. •. [For a discussion of this important point, see Savéant, J.-M. J. Am. Chem. Soc. 1987, 209, 6788.]
83. •+ by the procedure of Gschwind and Hasselbach in ref 37. (b) The facile 1,3-hydrogen shift in the prototypical propene radical cation has been predicted by Clark, T. J Am. Chem. Soc. 1987, 109, 6838. For the analogous conversion of 1-butene radical cation to the 2-butene isomer, see Roth, H. D Topics Curr. Chem. 1992, 163, 168.
84. •+ by the procedure of Gschwind and Hasselbach in ref 37. (b) The facile 1,3-hydrogen shift in the prototypical propene radical cation has been predicted by Clark, T. J Am. Chem. Soc. 1987, 109, 6838. For the analogous conversion of 1-butene radical cation to the 2-butene isomer, see Roth, H. D Topics Curr. Chem. 1992, 163, 168.
85. •+ by the procedure of Gschwind and Hasselbach in ref 37. (b) The facile 1,3-hydrogen shift in the prototypical propene radical cation has been predicted by Clark, T. J Am. Chem. Soc. 1987, 109, 6838. For the analogous conversion of 1-butene radical cation to the 2-butene isomer, see Roth, H. D Topics Curr. Chem. 1992, 163, 168.
86. •- allows sufficient time for the diffusive separation of the ion radical triad in Scheme 1; and it accounts for the observed second-order decay kinetics (compare Figure 6a). Otherwise the formulation in eq 12 predicts first-order decay kinetics of the spectral transients in the photochemical nitrations with TNM.
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88. Available from Aldrich Chemical Co. or readily prepared according to Liang, P. Org. Synth. 1955, 3, 803. Warning: Although we have never encountered difficulties, TNM is potentially hazardous.
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